JP2000229383A - Transparent coated molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain high abrasion-resistant surface characteristics by a method in which the inner layer contacting the outermost layer in transparent cured material layers is a layer of a specified active energy ray-curable coating composition and the outermost layer is a silica layer of a cured coating composition containing polysilazane. SOLUTION: In transparent cured material layers, the inner layer contacting the outermost layer is made a layer of a cured active energy ray-curable coating composition containing a polyfunctional compound (a) having at least two active energy ray-curable polymerizable functional groups and a hydrolyzable silyl group-containing compound (b), and the outermost layer is made a silica layer of a cured coating composition containing polysilazane (c). The active energy ray-curable polymerizable functional group of the compound (a) is especially preferably a (meth)acryloyl group, and a silane coupling agent, silazane, and others are named as the compound (b). As the polysilazane (c), perhydropolysilazane is preferable in view of its low baking temperature and the fineness of its cured coat.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent coated molded article having a transparent cured resin layer having excellent abrasion resistance, transparency, weather resistance, etc. on a transparent synthetic resin substrate. The inner layer in contact with the outermost layer of the material layer is a layer of a cured product derived from the active energy ray (especially ultraviolet) curable coating composition, and the outermost layer is a layer of silica derived from the coating composition forming silica. The present invention relates to a coated molded product.

[0002]

2. Description of the Related Art In recent years, as a transparent material replacing glass,
Transparent synthetic resin materials have been used. Above all, aromatic polycarbonate resin is excellent in crush resistance, transparency, light weight, easy processability, etc.
It is used in various areas as a large-area transparent member such as an arcade. Further, there is an example in which such a transparent synthetic resin material is used in place of glass (inorganic glass, hereinafter the same) for vehicles such as automobiles.

[0003] However, the transparent synthetic resin material has a drawback that the surface hardness is not sufficient to be used as a substitute for glass, and it is easily damaged or worn, so that the transparency is easily lost.

Therefore, many attempts have been made to improve the scratch resistance and abrasion resistance of aromatic polycarbonate resins.

[0005] A polymer curable compound having two or more polymerizable functional groups such as an acryloyl group in a molecule is applied to a substrate, and the polymer curable compound is cured by an active energy ray such as heat or ultraviolet rays, and the surface has scratch resistance. And ways to improve abrasion resistance (one of the most common methods).

[0006] A method in which a metal alkoxide compound such as a silicon-based compound is applied to a substrate and cured by heat in order to impart higher surface hardness to the substrate.

[0007] A method in which a mixture of a compound having an acryloyl group and colloidal silica is applied to a substrate and cured by an active energy ray such as ultraviolet rays to form a transparent cured layer having excellent scratch resistance (Japanese Patent Laid-Open No. 61-181809). Gazette).

[0008] A method using polysilazane instead of the silicon-based metal alkoxide compound, that is, a method in which polysilazane is applied to a substrate and cured by heat or the like (Japanese Patent Application Laid-Open No. 8-143689).

[0009] A method in which a protective film is formed on a plastic film and a polysilazane solution is applied on the surface to form a silica surface layer (Japanese Patent Application Laid-Open No. 9-39161).

[0010] A method in which a silicone-based thermopolymerized cured product is applied on an uncured product and a partially cured product of an ultraviolet-curable compound, irradiated with ultraviolet rays, and further heated and polymerized (JP-A-6-21)
2004 publication).

[0011] Forming an upper layer comprising an acrylic photopolymerization-curable coating and a polysiloxane composition having a silanol group, and an upper layer comprising a silicon-based thermopolymerization-curing coating;
A method in which an underlayer is cured by irradiation with ultraviolet rays and an upper layer is cured by heat treatment (Japanese Patent Application Laid-Open No. Hei 7-118425).

In the method (1), the composition for coating is relatively stable, and in particular, it can be cured by ultraviolet rays, so that the productivity is excellent. Further, even when the molded product is subjected to bending, no crack is generated in the cured film.

According to the method, a cured film having extremely excellent abrasion resistance can be formed. In the method of (1), by using colloidal silica in combination with the polymerizable curable compound, it is possible to achieve both high surface hardness and high productivity.

In the methods (1) to (4), polysilazane undergoes a condensation reaction or an oxidation reaction in the presence of oxygen, and is converted into a highly crosslinked product of silicon dioxide to form a silica coating.

According to the method, a silicone-based thermopolymerized cured layer is formed on the cured layer of the ultraviolet-curable compound.

In the method (1), the silanol groups of the upper layer and the silanol groups of the base layer (polysiloxane composition) are siloxane-bonded by a dehydration bonding reaction during polymerization of the upper layer (silicone thermosetting coating material), and the upper layer and the base layer are cured. And firmly bind.

It is known that the surface of a cured layer formed from the above polysilazane or thermosetting silicone resin has abrasion resistance. In particular, a silica coating derived from polysilazane has a high surface hardness similar to that of glass. have.

[0018]

However, in the above-mentioned method, since the cured film is made of only an organic substance, there is a limit in the expression level of the scratch resistance of the surface. , ~
The method (1) has a drawback that the cured film is liable to peel off or crack because of poor adhesion between the cured film and the substrate. In addition, the method described above was inferior to the method of applying the above-mentioned metal alkoxide compound to a base material and curing it by heat in terms of the surface scratch resistance level. This method has a problem that the outermost layer is inferior in abrasion resistance as compared with a cured layer made of polysilazane.

Accordingly, an object of the present invention is to provide a transparent coated molded article having a high abrasion resistant surface almost equivalent to that of inorganic glass and excellent in surface characteristics.

[0020]

In order to achieve the above object, the present inventors have determined that the outermost layer of the silica layer, such as abrasion resistance and abrasion resistance, has a different surface property between the silica layer and the inner layer. Considering that it is affected by the adhesiveness of the inner layer, the material of the inner layer which gives a silica layer having higher surface characteristics was examined. As a result, they found a material for the inner layer having high adhesion to the silica layer and sufficient adhesion to the base material, and completed the present invention.

That is, the present invention relates to a transparent synthetic resin substrate and a transparent cured product layer (A) provided on at least a part of the surface of the transparent synthetic resin substrate, the transparent cured product layer comprising at least an outermost layer and an inner layer. In the coated molded article, of the transparent cured product layer (A), the inner layer in contact with the outermost layer has a polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups and a hydrolyzable silyl compound. Group-containing compound (b)
Wherein the outermost layer is a silica layer which is a cured product of the coating composition (C) containing polysilazane (c). The present invention is to provide a transparent coated molded article to be formed.

In the present invention, the hydrolyzable silyl group-containing compound (b) having a high affinity for the silica layer is incorporated into the network of the inner layer to improve the adhesion between the inner layer and the silica layer. It has improved surface characteristics such as abrasion resistance and scratch resistance.

Further, the transparent cured product layer (A) in the present invention
Consists of at least two layers, an outermost layer and an inner layer,
The outermost layer of silica coating is not directly laminated on a relatively soft transparent synthetic resin base material, but is laminated on a hard transparent hardened material having high abrasion resistance. Therefore,
It is considered that the displacement of the outermost layer due to an external force applied to the transparent coated molded article to damage the transparent coated article becomes small, so that it is possible to obtain surface properties higher than those provided by a normal inorganic coating.

That is, according to the present invention, although the outermost layer is a coating mainly composed of an inorganic substance, the outermost layer is sufficiently adhered to the inner layer and consequently to the transparent synthetic resin substrate (hereinafter simply referred to as the substrate). In addition, it is possible to provide a transparent synthetic resin molded article having a transparent cured material layer having surface abrasion resistance equal to or close to that of glass.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the transparent cured product layer (A) is in direct contact with the transparent cured product layer forming the outermost layer (hereinafter referred to as the transparent cured product outermost layer) and the transparent cured product outermost layer. It is composed of at least two layers of a transparent cured product layer (hereinafter, referred to as a transparent cured product inner layer).

The inner layer of the transparent cured product is a polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups (hereinafter referred to as a polyfunctional compound (a)).
Cured product of an active energy ray-curable coating composition (B) (hereinafter, referred to as a coating composition (B)) comprising a hydrolyzable silyl group-containing compound (b) (hereinafter, referred to as a silyl group-containing compound (b)) Layer.

In the present invention, a second inner layer made of a thermoplastic resin such as a thermoplastic acrylic resin or another synthetic resin such as an adhesive is further provided between the substrate and the inner layer of the transparent cured product. It may be. In this case, the second inner layer is preferably made of a composition having sufficient adhesion to both (the base material and the inner layer of the transparent cured product).

In the present invention, the transparent cured product inner layer comprises:
It has the effect of improving the adhesion between the substrate or the second inner layer on the substrate and the outermost layer, and improving the surface properties of the outermost layer by reducing the displacement of the outermost layer due to external force.

That is, the coating composition (B) comprises a base material or a second
A polyfunctional compound (a) for the purpose of increasing the adhesion to the inner layer and reducing the displacement of the outermost layer due to external force, and a silyl group-containing compound (b) for the purpose of increasing the adhesion to the outermost layer
It is a composition containing.

In the present invention, in order to obtain an inner layer of a transparent hardened material having higher abrasion resistance, the coating composition (B) is used.
May be mixed with colloidal silica having an average particle diameter of 200 nm or less to form a cured product containing colloidal silica.

That is, in the present invention, the inner layer of the transparent cured product has a haze value (a haze value after the abrasion test and a haze value before the abrasion test) after the abrasion resistance test (100 times of tests) according to JIS-R3212. Difference) is preferably 15% or less,
More preferably, the haze value is 10% or less, particularly 5% or less.

Description of Polyfunctional Compound (a) Hereinafter, in the present specification, an acryloyl group and a methacryloyl group are collectively referred to as a (meth) acryloyl group. The same applies to expressions such as (meth) acryloyloxy group, (meth) acrylic acid, and (meth) acrylate.

In the present invention, the polyfunctional compound (a)
Is a mixture of one or more polyfunctional compounds.

When a plurality of types of polyfunctional compounds are used,
It may be a different compound in the same category, or a different compound in the category. For example, a combination of different compounds each of which is acrylic urethane, or a combination of which one is acrylic urethane and the other is an acrylate compound having no urethane bond may be used.

Further, a monofunctional compound having one polymerizable functional group polymerizable by an active energy ray (hereinafter, referred to as a monofunctional compound) may be contained together with the polyfunctional compound.

When the above monofunctional compound is used in the coating composition (B), the ratio of the monofunctional compound to the total of the polyfunctional compound (a) and the monofunctional compound is not particularly limited, It is preferably 0 to 60% by weight, more preferably 0 to 30% by weight.

If the proportion of the monofunctional compound is too large, the hardness of the cured coating film may decrease, and the abrasion resistance may be insufficient.

As the monofunctional compound, a compound having a (meth) acryloyl group is preferable, and a compound having an acryloyl group is particularly preferable. Further, the monofunctional compound may have a functional group such as a hydroxyl group and an epoxy group. Preferred monofunctional compounds are (meth) acrylates, ie (meth) acrylates.

Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate
Examples include acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and glycidyl (meth) acrylate.

The active energy ray-curable polymerizable functional group of the polyfunctional compound (a) includes α, β-unsaturated groups such as (meth) acryloyl group, vinyl group and allyl group and groups having the same. Among them, a (meth) acryloyl group is preferred, and among the above groups and compounds, more preferred are those having an acryloyl group, for example, an acryloyloxy group, acrylic acid, acrylate and the like.

The term “polyfunctional” means that the above-mentioned polymerizable functional group is 2
In the present invention, the upper limit of the number of the polymerizable functional groups contained in one molecule is not particularly limited, but is usually 2 to 50, and particularly preferably 3 to 30. .

The type of the polymerizable functional group contained in one molecule is not particularly limited, and may be one type or two or more types.

That is, the polyfunctional compound (a) is selected from one or more polymerizable functional groups selected from (meth) acryloyl groups, and among them, compounds having two or more acryloyl groups which are more easily polymerized by ultraviolet rays. It is particularly preferable to use a polyester having (meth) acrylic acid and a compound having two or more (meth) acryloyloxy groups, that is, a compound having two or more hydroxyl groups such as a polyhydric alcohol.

Further, since the cured product of the coating composition (B) can exhibit sufficient abrasion resistance, at least one of the polyfunctional compounds (a) is one of the polyfunctional compounds (a). Parts (preferably at least 30% by weight, particularly preferably 50% by weight).
% By weight or more).

In addition to the above polymerizable functional groups, for example,
Hydroxyl group, carboxyl group, halogen atom, urethane bond, ether bond, ester bond, thioether bond,
It may have various functional groups and bonds such as an amide bond and a diorganosiloxane bond. In such a case, the compound (meth) acryloyl group-containing compound having a urethane bond (so-called acrylic urethane) has no urethane bond. (Meth) acrylate compounds are preferred.

The above (meth) acryloyl group-containing compound having a urethane bond (hereinafter referred to as acrylic urethane)
Examples of the compound include: a compound having a (meth) acryloyl group and a hydroxyl group (X
Reaction product of 1) with a compound having two or more isocyanate groups (hereinafter, referred to as polyisocyanate) -Production of the above compound (X1) with compound (X2) having two or more hydroxyl groups and polyisocyanate Compounds: Examples include reaction products of the compound (X3) having a (meth) acryloyl group and an isocyanate group with the compound (X2).

In each of the above reaction products, a hydroxyl group may be present, but it is preferable that an isocyanate group is not present.

Therefore, in the production of the above reaction product, the total number of moles of hydroxyl groups in all the reaction raw materials is preferably equal to or larger than the total number of moles of isocyanate groups.

That is, the compound (X1) includes the following. A compound having one (meth) acryloyl group and one hydroxyl group, a compound having two or more (meth) acryloyl groups and one hydroxyl group, a compound having one (meth) acryloyl group and two or more hydroxyl groups, ) Compounds having two or more acryloyl groups and two or more hydroxyl groups.

Specifically, 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol di (meth) acrylate and the like are mentioned in this order. These are monoesters of a compound having two or more hydroxyl groups and (meth) acrylic acid, or polyesters having one or more hydroxyl groups.

A ring-opening reaction product of a compound having at least one epoxy group with (meth) acrylic acid; In this case, by the reaction between the epoxy group and (meth) acrylic acid, the epoxy group is opened to form an ester bond and a hydroxyl group to form a compound having a (meth) acryloyl group and a hydroxyl group. Alternatively, the epoxy group of the compound having one or more epoxy groups may be opened to form a hydroxyl group-containing compound, which may be converted to a (meth) acrylate.

That is, polyepoxides, which are so-called epoxy resins, are preferred. For example, compounds having two or more glycidyl groups such as polyhydric phenols-polyglycidyl ether (specifically, bisphenol A-diglycidyl ether) And alicyclic epoxy compounds are preferred.

A reaction product of a (meth) acrylate having an epoxy group and a compound having a hydroxyl group or a carboxyl group. The (meth) acrylate having an epoxy group includes, for example, glycidyl (meth) acrylate.

The following are examples of the polyisocyanate. -Normal monomeric polyisocyanate. For example, 2,6-tolylene diisocyanate, 2,4-
Tolylene diisocyanate, methylene bis (4-phenyl isocyanate) [MDI], hexamethylene diisocyanate, isophorone diisocyanate, transcyclohexane-1,4-diisocyanate, xylylene diisocyanate [XDI], hydrogenated XDI, hydrogenated MDI
And the like (abbreviations in []) are preferred, but non-yellowing-modified polyisocyanates (polyisocyanates not having an isocyanate group directly bonded to an aromatic nucleus) are preferred. Specifically, aliphatic polyisocyanates such as hexamethylene diisocyanate And alicyclic polyisocyanates such as isophorone diisocyanate and aromatic polyisocyanates such as xylylene diisocyanate.

Further, as described later, these multimers and denatured products are also preferable. -Prepolymer-like compounds such as multimers, modified polyisocyanates or isocyanate group-containing urethane prepolymers. Examples of the polymer include a trimer (isocyanurate-modified), dimer, and carbodiimide-modified. Examples of the modified include urethane-modified products obtained by denaturation with a polyhydric alcohol such as trimethylolpropane. There are a buret modified product, an allohanate modified product, a urea modified product and the like.

Examples of the prepolymer compound include isocyanate group-containing urethane prepolymers obtained by reacting polyols such as polyether polyols and polyester polyols described below with polyisocyanates. Two or more isocyanates may be used in combination.

Next, examples of the compound (X2) include the following. Polyhydric alcohol aliphatic polyhydric alcohol, or alicyclic polyhydric alcohol or polyhydric alcohol having an aromatic nucleus,
Polyhydric alcohols having 20 hydroxyl groups are preferable, and polyhydric alcohols having 2 to 15 hydroxyl groups are particularly preferable.

The polyhydric alcohol having an aromatic nucleus includes
For example, an alkylene oxide adduct of a polyhydric phenol or a ring-opened product of a polyepoxide having an aromatic nucleus such as a polyhydric phenol-polyglycidyl ether may be used.

That is, examples of the polyhydric alcohol include ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, and the like.
Neopentyl glycol, cyclohexanediol, dimethylolcyclohexane, trimethylolpropane,
Glycerin, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tris (2-hydroxyethyl) isocyanurate, tris (2-hydroxypropyl) isocyanurate, bisphenol A-
There are ring-opened products of diglycidyl ether and ring-opened products of vinylcyclohexene dioxide.

Polyols higher in molecular weight than polyhydric alcohols Polyether polyols, polyester polyols, polyether ester polyols, polycarbonate polyols and the like can be mentioned. Also, a hydroxyl group-containing vinyl polymer can be used as the polyol.

The hydroxyl group-containing vinyl polymer includes:
For example, there is a copolymer of a hydroxyl group-containing monomer such as allyl alcohol, vinyl alcohol, hydroxyalkyl vinyl ether and hydroxyalkyl (meth) acrylate and a hydroxyl group-free monomer such as olefin.

That is, specific examples of the above polyol include:
Polyethylene glycol, polypropylene glycol,
Bisphenol A-alkylene oxide adducts, polyether polyols such as polytetramethylene glycol,
Polyester polyol obtained by ring-opening polymerization of a cyclic ester such as poly ε-caprolactone polyol, adipic acid, sebacic acid, phthalic acid, maleic acid, fumaric acid,
Azelaic acid, a polyester polyol obtained by the reaction of a polybasic acid such as glutaric acid and the polyhydric alcohol,
Polycarbonate diols obtained by the reaction of 1,6-hexanediol and phosgene are exemplified.

The above-mentioned polyhydric alcohols and polyols may be used in combination of two or more. Then, the compound (X
Examples of 3) include 2-isocyanatoethyl (meth) acrylate and methacryloyl isocyanate.

As the (meth) acrylate compound having no urethane bond, a polyester of a compound having two or more hydroxyl groups and a (meth) acrylic acid similar to the compound (X2) is preferable.

As the compound having two or more hydroxyl groups, the above-mentioned polyhydric alcohols and polyols are preferable.

The reaction product of a compound having two or more epoxy groups with (meth) acrylic acid is (meth)
Acrylic ester compounds are also preferred.

As a compound having two or more epoxy groups, there is a polyepoxide called an epoxy resin. For example, commercially available epoxy resins such as glycidyl ether type polyepoxide and alicyclic type polyepoxide can be used.

Specific examples of the polyfunctional compound having no urethane bond include the following compounds.

(Meth) of the following aliphatic polyhydric alcohols
Acrylate. 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-
Hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate.

The following (meth) acrylates of the following polyhydric alcohols or phenols having an aromatic nucleus or a triazine ring. Tris (2- (meth) acryloyloxyethyl) isocyanurate, bis (2- (meth) acryloyloxyethyl) -2-hydroxyethyl isocyanurate, tris (2- (meth) acryloyloxypropyl) isocyanurate, bis (2 -(Meth) acryloyloxyethyl) bisphenol A, bis (2- (meth) acryloyloxyethyl) bisphenol S, bis (2-
((Meth) acryloyloxyethyl) bisphenol F, bisphenol A dimethacrylate.

The following (meth) acrylates of hydroxyl group-containing compounds-alkylene oxide adducts, (meth) acrylates of hydroxyl group-containing compounds-caprolactone adducts, and (meth) acrylates of polyoxyalkylene polyols. Here, EO represents ethylene oxide, and PO represents propylene oxide.

Trimethylolpropane-EO adduct tri (meth) acrylate, trimethylolpropane-P
O adduct tri (meth) acrylate, dipentaerythritol-caprolactone adduct hexa (meth) acrylate, tris (2-hydroxyethyl) isocyanurate-caprolactone adduct tri (meth) acrylate, tris (2-hydroxyethyl) ) Tri (meth) acrylate of isocyanurate-caprolactone adduct.

Accordingly, specific preferred polyfunctional compounds (a) are the following polyfunctional compounds having no urethane bond with acrylic urethane.

Examples of acrylurethane include acrylic urethane which is a reaction product of pentaerythritol and its polymer polypentaerythritol with polyisocyanate and hydroxyalkyl (meth) acrylate, or hydroxyl group-containing polypentaerythritol and polypentaerythritol. Acrylic urethane which is a reaction product of a (meth) acrylate and a polyisocyanate,
Functional or higher (preferably 4 to 20 functional) compounds.

The polyfunctional compounds having no urethane bond include pentaerythritol-based poly (meth) acrylate and isocyanurate-based poly (meth) acrylate.

The above pentaerythritol-based poly (meth)
The acrylate refers to a polyester of pentaerythritol or polypentaerythritol with (meth) acrylic acid (preferably having a functionality of 4 to 20).

The above-mentioned isocyanurate-based poly (meth) acrylate refers to tris (hydroxyalkyl) isocyanurate, or an adduct obtained by adding 1 to 6 mol of caprolactone or alkylene oxide to 1 mol of the same, and (meth) acrylic acid. Polyester with acid (2- or 3-functional).

It is also preferable to use these preferred polyfunctional compounds in combination with other bifunctional or higher polyfunctional compounds (particularly polyhydric alcohol poly (meth) acrylate).
These preferable polyfunctional compounds are preferably at least 30% by weight, particularly preferably at least 50% by weight, based on the total polyfunctional compound (a).

Description of Hydrolyzable Silyl Group-Containing Compound (b) In the present invention, in order to increase the adhesion between the coating composition (B) and the coating composition (C), the coating composition (B) And a hydrolyzable silyl group-containing compound (b). As the hydrolyzable silyl group-containing compound (b),
There are silane coupling agents and silazanes represented by the following chemical formula 1.

[0080]

Embedded image

In the above formula 1, examples of X include an alkoxy group, an acyl group, an amino group, an isocyanate group and the like, and the most preferred is an alkoxy group having 1 to 4 carbon atoms. R ¹ is a hydrocarbon group having 2 to 8 carbon atoms, most preferably an alkylene group.
R ² is an alkyl group having 1 to 4 carbon atoms, Z is a (meth) acryloyl group, a mercapto group, an amino group,
Epoxy, vinyl and isocyanate groups are exemplified.

In the present invention, the addition of the silane coupling agent causes the functional group represented by Z to polymerize or react with the functional group of the polyfunctional compound (a) in the inner layer. It is considered that the inner layer and the outermost layer are more closely adhered to each other by the dehydration reaction between the functional group represented and the polysilazane in the outermost layer. On the other hand, in the case of silazane, it is considered that the silazane and the polysilazane in the outermost layer are combined by a dehydration reaction, and the adhesion is similarly improved.

That is, the silyl group-containing compound (b) is
Specifically, compounds such as silazane and a silane coupling agent are preferable. For example, one kind or a plurality of kinds of compounds selected from them may be used such as a combination of silazane and a silane coupling agent.

Examples of the silazane include 1,1,3,3-tetramethyldisilazane, hexamethyldisilazane, 1,3
-Bis (chloromethyl) -1,1,3,3-tetramethyldisilazane, heptamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, hexaphenylcyclodisilazane, 1,1,3,3,5,5
-Hexamethylcyclotrisilazane, 1,1,3,3
5,5,7,7-octamethylcyclotetrasilazane,
Perhydropolysilazane, methyl group-containing polysilazane, or the like can be used.

As the silane coupling agent, for example,
The following can be used: -(Meth) acryloyloxy group-containing silanes: 3-
(Meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane and the like.

Amino group-containing silanes: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane,
3-ureidopropyltriethoxysilane, N- (N-
Vinylbenzyl-2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like.

Mercapto group-containing silanes: 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane and the like.

Epoxy group-containing silanes: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane and the like.

Isocyanate group-containing silanes: 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane and the like.

The amount of the silyl group-containing compound (b) in the coating composition (B) is 0.01 to 100 parts by weight of the curable component (the total of the polyfunctional compound (a) and the monofunctional compound). -200 parts by weight, particularly preferably 0.1-100 parts by weight.

In the present invention, in order to cure the polyfunctional compound (a), the coating composition (B) usually contains a photopolymerization initiator.

As the photopolymerization initiator, known photopolymerization initiators can be used, and a plurality of photopolymerization initiators may be used in the transparent cured material layer. However, commercially available photopolymerization initiators are particularly preferable.

Examples of the photopolymerization initiator include arylketone photopolymerization initiators (eg, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethyl ketals, benzoylbenzoates, α-acyloxime esters), sulfur-containing photopolymerization initiators (eg, sulfides, thioxanthones, etc.), acylphosphine oxide photopolymerization initiators, diacylphosphine oxide photopolymerization initiators, and other photopolymerization initiators In particular, an acylphosphine oxide-based photopolymerization initiator and a diacylphosphine oxide-based photopolymerization initiator are preferably used. Also, the photopolymerization initiator,
It may be used in combination with a photosensitizer such as an amine.

That is, specific examples of the photopolymerization initiator include the following compounds.

4-phenoxydichloroacetophenone,
4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl)
-2-hydroxy-2-methylpropan-1-one, 1
-(4-dodecylphenyl) -2-methylpropane-1
-One, 1- {4- (2-hydroxyethoxy) phenyl} -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2
-Methyl-1- {4- (methylthio) phenyl} -2-
Morpholinopropan-1-one.

Benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 3,3 ', 4,4'-tetrakis (t-
Butylperoxycarbonyl) benzophenone, 9.1
0-phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4,4'-diethylisophthalophenone, α-acyloxime ester, methylphenylglyoxylate.

4-benzoyl-4'-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone.

2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide , Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.

The amount of the photopolymerization initiator in the coating composition (B) is determined by the amount of the curable component (the polyfunctional compound (a)).
And the monofunctional compound) in an amount of 0.0 with respect to 100 parts by weight.
The amount is preferably 1 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight.

The coating composition (B) may contain, if necessary, various compounding agents (eg, light stabilizers, ultraviolet absorbers, antioxidants, thermal polymerization inhibitors, etc.) in addition to the above basic components. Agents, leveling agents, defoamers, thickeners, antisettling agents, pigments, dispersants, antistatic agents, surfactants such as antifoggants,
A curing catalyst selected from acids, alkalis and salts).

In the coating composition (B) -containing coating liquid for forming a layer of the coating composition (B), the solvent is usually an essential component, and the polyfunctional compound (a) is particularly low. Solvents are used unless they are liquids of viscosity.

As the solvent, the polyfunctional compound (a)
Solvents usually used for the coating composition (B) containing as a curing component can be used. Although a dispersion medium of the raw material colloidal silica described below can be used as a solvent as it is, it is preferable to select and use an appropriate solvent depending on the type of the base material.

That is, for example, the above-mentioned solvents used for the hydrolysis for modifying the colloidal silica described below are used.
Solvents such as lower alcohols, ketones, ethers, and cellosolves, esters such as n-butyl acetate and diethylene glycol monoacetate, halogenated hydrocarbons, hydrocarbons, and the like. Lower alcohols, cellosolves, esters, mixtures thereof, and the like are suitable for coating the aromatic polycarbonate resin.

The amount of the solvent can be appropriately changed depending on the required viscosity of the composition, the desired thickness of the cured film, the conditions of the drying temperature, and the like. 100 times or less, preferably 0.1 to 50 times
Use double weight.

The active energy ray for curing the coating composition (B) is not particularly limited, but ultraviolet rays are preferred. Xenon lamps, pulsed xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, tungsten lamps and the like can be used as the ultraviolet light source.

The layer thickness of the cured product formed using the coating composition (B) is preferably 1 to 50 μm,
More preferably, it is 2 to 30 μm.

When the thickness of the layer is more than 50 μm, the curing by the active energy ray becomes insufficient, and the adhesion to the substrate is easily damaged. When the thickness is less than 1 μm, the abrasion resistance of the layer may be insufficient. In addition, there is a possibility that the outermost layer formed on this layer cannot sufficiently exhibit abrasion resistance and scratch resistance.

In the present invention, colloidal silica having an average particle diameter of 200 nm or less may be added to the coating composition (B) in order to increase the abrasion resistance and hardness of the inner layer of the transparent cured product which is in direct contact with the outermost layer. .

The above colloidal silica has an average particle size of 1 to 10.
It is preferably 100 nm, particularly preferably 1 to 50 nm.

The amount of the colloidal silica added is as follows:
It is preferably at least 5 parts by weight, more preferably at least 10 parts by weight, per 100 parts by weight of the curable component (total of the polyfunctional compound (a) and the monofunctional compound) of the transparent cured material layer.

When the addition amount is small, it is difficult to obtain sufficient abrasion resistance. When the addition amount is too large, clouding (haze) tends to occur in the coating, and the obtained transparent coated molded article is subjected to hot bending. In the case of performing secondary processing such as the above, there arises a problem that cracks are easily generated.

Therefore, the upper limit of the amount of colloidal silica in the curable component of the transparent cured product layer is preferably 300 parts by weight based on 100 parts by weight of the curable component.

That is, the most preferable amount of the colloidal silica is 50 to 250 parts by weight based on 100 parts by weight of the curable component.

As the colloidal silica, a surface-unmodified colloidal silica can be used, but a surface-modified colloidal silica (hereinafter referred to as a modified colloidal silica) is preferably used.

By using the surface-modified colloidal silica, the dispersion stability of the colloidal silica in the coating composition (B) is improved, and the adhesion between the colloidal silica and the polyfunctional compound (a) is improved. Is improved.

The average particle size of the colloidal silica fine particles is considered to be substantially unchanged or slightly increased by the modification, but the average particle size of the obtained modified colloidal silica is considered to be in the above range.

Hereinafter, the modified colloidal silica will be described. Various dispersion media are known as the dispersion medium of the colloidal silica, and the dispersion medium of the raw material colloidal silica is not particularly limited, and the modification can be performed by changing the dispersion medium if necessary. Although the dispersion medium can be changed after the modification, the dispersion medium of the raw material colloidal silica, the dispersion medium of the modified colloidal silica, and the medium of the cured composition of the transparent cured material layer are, for reasons such as easiness of production, Preferably, they are all the same medium (solvent).

As such a medium, a conventional solvent for coating which is a solvent having a relatively low boiling point is preferable from the viewpoint of drying properties and the like, for example, water, methanol, ethanol, isopropanol, n-butanol, 2-methylpropanol. ,
Lower alcohols such as 4-hydroxy-4-methyl-2-pentanone and ethylene glycol.

Cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve. Examples thereof include dimethylacetamide, toluene, xylene, methyl acetate, ethyl acetate, butyl acetate, and acetone. Of these, organic solvents are preferable, and among the organic solvents, alcohols and cellosolves are more preferable.

[0120] An integrated product of colloidal silica and a dispersion medium in which the colloidal silica is dispersed is hereinafter referred to as a colloidal silica dispersion.

The modification of the colloidal silica is preferably performed using a compound having a hydrolyzable silicon group or a silicon group to which a hydroxyl group is bonded (hereinafter, referred to as a modifier).

That is, the hydrolysis of the hydrolyzable silicon groups produces silanol groups, which react with and bind to the silanol groups which are considered to be present on the colloidal silica surface, and the modifier is attached to the colloidal silica surface. It is thought to be combined.

The above-mentioned modifying agents may be used in combination of two or more kinds. As described later, the modifying product obtained by previously reacting two kinds of modifying agents having reactive functional groups reactive with each other is modified. It can also be used as an agent.

That is, the modifier has two or more hydrolyzable silicon groups, a substance having a silanol group, a partially hydrolyzed condensate of a compound having a hydrolyzable silicon group, or a compound having a silanol group. A partial condensate of the compound can be used. Preferably, a compound having one hydrolyzable silicon group is used (a partial hydrolysis condensate may be generated in the modification process). More preferably, a compound having an organic group bonded to a silicon atom and at least one of the organic groups being an organic group having a reactive functional group is used.

Examples of the reactive functional group include an amino group, a mercapto group, an epoxy group and a (meth) acryloyloxy group.

The organic group to which the reactive functional group is bonded is preferably an alkylene group having 8 or less carbon atoms or a phenylene group, excluding the reactive functional group, particularly an alkylene group having 2 to 4 carbon atoms (particularly polymethylene). Group) is preferred.

Accordingly, specific modifiers can be classified according to the type of the reactive functional group. For example, the above-mentioned silane coupling agents such as (meth) acryloyloxy group-containing silanes, amino group-containing silanes, and mercapto group Examples include compounds such as silanes containing silanes, silanes containing epoxy groups, and silanes containing isocyanate groups.

The reaction products obtained by preliminarily reacting two types of modifiers having reactive functional groups reactive with each other include, for example, a reaction product of an amino group-containing silane and an epoxy group-containing silane.・ Reaction product of amino group-containing silanes and (meth) acryloyloxy group-containing silanes ・ Reaction product of epoxy group-containing silanes and mercapto group-containing silanes ・ Reaction of two molecules of mercapto group-containing silanes And the like.

In the modification of the colloidal silica, the amount of the modifier used is not particularly limited, but 100 parts by weight of the colloidal silica (solid content in the dispersion) and the modifier 1 are used.
-100 parts by weight are suitable.

When the amount of the modifying agent is less than 1 part by weight, the effect of surface modification is hardly obtained, and when it exceeds 100 parts by weight, the unreacted modifying agent or the hydrolyzate of the modifying agent not supported on the surface of the colloidal silica is used. A large amount of condensate is generated, and when the transparent coating layer (cured composition) is cured, they act as a chain transfer agent or act as a plasticizer of the cured film, which may reduce the hardness of the cured film. .

The modification of the colloidal silica is usually carried out by bringing the above-mentioned modifier into contact with the colloidal silica in the presence of a catalyst and hydrolyzing it.

Examples of the catalyst include acids and alkalis. Preferably, an acid selected from inorganic acids and organic acids is used.

The inorganic acids include, for example, hydrohalic acids such as hydrochloric acid, hydrofluoric acid, and hydrobromic acid; sulfuric acid, nitric acid, and phosphoric acid; and the organic acids include formic acid, acetic acid, oxalic acid, and acrylic acid. , Methacrylic acid and the like can be used.

The reaction temperature is preferably from room temperature to the boiling point of the solvent to be used, and the reaction time depends on the temperature, but may be 0.5 to 0.5.
It is preferable to carry out in a range of from 24 hours.

Description of Coating Composition (C) The coating composition (C) contains polysilazane (c). The polysilazane (c) is composed of a polymer having a chain, cyclic or cross-linked structure, or a mixture of the above plural structures in the molecule, and forms silica having a more dense structure, so that the outermost layer having excellent surface properties is formed. Obtainable.

Examples of the polysilazane (c) include polysilazane (perhydropolysilazane) substantially free of an organic group, polysilazane in which a hydrolyzable group such as an alkoxy group is bonded to a silicon atom, and an organic group such as an alkyl group in a silicon atom. Examples thereof include polysilazane having a group bonded thereto. Perhydropolysilazane is particularly preferable in terms of low firing temperature and denseness of a cured film after firing. In addition, a cured product in which polysilazane is sufficiently cured becomes silica containing almost no nitrogen atoms.

The molecular weight of the polysilazane (c) is preferably a number average molecular weight of 200 to 50,000. If the number average molecular weight is less than 200, it is difficult to obtain a uniform cured film even when baked, and if the number average molecular weight is more than 50,000, it becomes difficult to dissolve in a solvent, and the coating composition (C) may become viscous. It is not preferable because there is.

The coating solution for forming the layer of the coating composition (C) usually contains a material for dissolving polysilazane.

Solvents for dissolving polysilazane include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, ethers such as aliphatic ethers and alicyclic ethers. Can be used.

Specifically, hydrocarbons such as pentane, hexane, isohexane, methylpentane, heptane, isoheptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, etc. Halogenated hydrocarbons such as methylene, chloroform, carbon tetrachloride, bromoform, 1,2-dichloroethane, 1,1-dichloroethane, trichloroethane, tetrachloroethane, ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, dioxane, dimethyl dioxane, tetrahydrofuran And ethers such as tetrahydropyran.

When the above-mentioned solvent is used, plural kinds of solvents may be mixed and used for adjusting the solubility of polysilazane and the evaporation rate of the solvent.

The amount of the solvent to be used can be appropriately selected depending on the coating method to be employed, the structure of polysilazane, the average molecular weight, and the like. However, the amount of the solvent may be adjusted to a solid content of 0.5 to 80% by weight. preferable.

In order to cure polysilazane to silica, heating usually called calcination is required. However, in the present invention, the calcination temperature is limited because the base material is a synthetic resin.

In the present invention, the heat resistance of the cured product of the coating composition (B) is generally higher than that of the substrate. However, in some cases, the heat resistance of the cured product of the coating composition (B) may be lower than the heat resistance of the base material, in which case it is necessary to fire at a temperature lower than the heat resistance temperature of the cured product. .

Therefore, in the present invention, the firing temperature of polysilazane is preferably 180 ° C. or lower when a general synthetic resin such as an aromatic polycarbonate resin is used as a base material.

In the present invention, when the polysilazane is cured at a low temperature, it is preferable to use a catalyst, and curing at room temperature is possible depending on the type and amount of the catalyst. The atmosphere for curing is preferably an atmosphere in which oxygen is present, such as in air.

As the catalyst, it is preferable to use a catalyst capable of curing polysilazane at a lower temperature.
As such a catalyst, known catalysts can be used. For example, fine particles of metals such as gold, silver, palladium, platinum and nickel described in JP-A-7-196886, and JP-A-5-93275 Examples thereof include those carboxylic acid complexes described in the gazette.

When a catalyst is used, the catalyst is not added to the polysilazane solution, but is disclosed in JP-A-9-3.
As described in JP-A No. 1333, a method of directly contacting a coated molded product with a catalyst solution, specifically, an aqueous amine solution or the like, or exposing the coated molded product to a vapor thereof for a certain period of time can be mentioned.

The coating composition (C) may further contain, if necessary, stabilizers such as an ultraviolet absorber, a light stabilizer and an antioxidant.
Surfactants such as a leveling agent, an antifoaming agent, a thickener, an antisettling agent, a pigment, a dispersant, an antistatic agent, and an antifogging agent may be appropriately blended and used.

In the present invention, the thickness of the cured product layer formed using the coating composition (C) is 0.05 to 10 μm.
And more preferably 0.1 to 3 μm
It is.

If the thickness of the outermost layer is more than 10 μm, further improvement in surface properties such as abrasion resistance cannot be expected, and the layer becomes brittle and the outermost layer may be cracked even by slight deformation of the coated molded product. When the thickness is less than 0.05 μm, the outermost layer may not sufficiently exhibit abrasion resistance and abrasion resistance.

The method of forming two transparent cured material layers (transparent cured material layer (A)) formed by using the above two types of coating compositions (B) and (C) is as follows. ,
For example, a normal coating method such as applying the coating composition (B) on the base material and curing it, and then applying and curing the coating composition (C) on the surface of the cured product is adopted. can do.

In the case of having the second inner layer, after coating, it is dried to remove the solvent (when the composition of the second inner layer contains a solvent), and then the coating composition (B) is added. The used layer is cured by irradiating ultraviolet rays or the like, and the coating composition (C)
Is cured by heating, leaving it at room temperature, or exposing it to the vapor of a curing catalyst solution of the coating composition (C).

The means for applying the coating composition is not particularly limited, and examples thereof include a dip method, a flow coat method, a spray method, a bar coat method, a gravure coat method, a roll coat method, a blade coat method, and an air knife coat method. Known methods such as a spin coating method, a spin coating method, a slit coating method, and a microgravure coating method can be employed.

The combination (timing) of the curing of the coating composition (B) and the coating and curing of the coating composition (C) includes the following methods.

1) A method of applying the coating composition (B) and then irradiating a sufficient amount of active energy rays to sufficiently cure the composition, and then applying the composition (C) thereon ( Method described above).

2) After coating the coating composition (B) to form an uncured layer of the coating composition (B), the coating composition (C) was coated on the uncured layer. Forming a layer of the uncured material of the coating composition (C), and then irradiating a sufficient amount of active energy rays to terminate the curing of the uncured material of the coating composition (B). In this case, the uncured product of the coating composition (C) is cured by leaving the uncured product of the coating composition (B) at room temperature or by being exposed to the vapor of a catalyst solution.

3) After coating the coating composition (B), the coating composition is irradiated once with a minimum active energy ray (typically, an irradiation amount of up to about 300 mJ / cm ² ) to be in a touch-dry state. After forming the layer of the partially cured product of (B), the coating composition (C) is applied on the partially cured product layer to form an uncured layer of the coating composition (C). A method of irradiating a sufficient amount of active energy rays to terminate the curing of the uncured material of the coating composition (B). The method of curing the uncured material of the coating composition (C) is the same as in the case 2) above.

In the present invention, the above method 2) or 3) is preferable in order to increase the interlayer adhesion between the two cured product layers.

However, in the case of the method 2), if the dipping method is used as a method of applying the coating composition (C), the component of the uncured material of the coating composition (B) is changed to the coating composition (C). Therefore, there is a restriction that coating by such a dipping method is not suitable because the dipping liquid may be contaminated.

In the present invention, according to the above-described method,
A transparent cured product layer (A) comprising at least two layers as described above is formed on both surfaces or one surface of the substrate.

The transparent coated molded article of the present invention is characterized in that its surface properties such as abrasion resistance and abrasion resistance are almost equal to those of glass. It can be used for various purposes such as use as a material.

In the present invention, when manufacturing a bent molded product (such as a window material for a vehicle), the transparent cured material layer (A) can be formed using a base material that has been bent in advance. It is preferable to bend the coating composition (C) in a state where a layer of the uncured product or the partially cured product is formed on the partially cured product layer of the coating composition (B).

That is, when a base material that has been bent in advance is used, it may be difficult to form each layer by coating and curing, and a layer of a cured product of the coating composition (B) may be formed. The substrate can be bent by hot bending or the like. However, when a layer of the cured product of the coating composition (C) is formed, the cured product is hard, so that it becomes difficult to bend. Because.

After the bending, or almost at the same time as the bending, the uncured or partially cured product of the coating composition (C) is cured, whereby the intended bent coated article can be obtained.

Since the bending is performed in a heated state,
The uncured or partially cured product of the coating composition (C) is cured by heating during bending, but usually the uncured or partially cured product of the coating composition (C) is compared with the time required for bending. Since the time required for curing the cured product is long, the coating composition (C)
It is unlikely that the bending process will be difficult due to the hardening.

Accordingly, the bent molded article of the present invention comprises a layer of a partially cured product of the coating composition (B) on a substrate and an uncured product of the coating composition (C) on the surface of the layer. After forming the layers of the partially cured product, the substrate having these layers is bent, and then the uncured or partially cured product of the coating composition (C) and partially cured of the coating composition (B) It can be produced by curing an object.

Specifically, for example, after forming a layer of an uncured material or a partially cured material of the coating composition (C), the substrate is heated to the heat softening temperature of the substrate for about 5 minutes, and then subjected to bending. . Thereafter, the present invention is maintained at a temperature at which the uncured or partially cured product of the coating composition (C) can be cured or left at room temperature, or cured by exposure to the vapor of a curing catalyst solution of the coating composition (C). Can be obtained.

By adopting the above-mentioned method, the base material is deformed before the coating composition (C) is sufficiently cured, and thereafter a hard silica layer is formed. No failures occur.

The material of the transparent synthetic resin substrate in the present invention is not particularly limited, and various transparent synthetic resins can be used. For example, aromatic polycarbonate resin,
Transparent synthetic resins such as polymethyl methacrylate resin (acrylic resin) and polystyrene resin may be mentioned, but a substrate made of an aromatic polycarbonate resin is particularly preferably used.

The transparent synthetic resin substrate may be a molded substrate, for example, a sheet substrate such as a flat plate or a corrugated plate, a film substrate, a substrate molded into various shapes, or at least a surface. Examples of the layer include a laminate made of various transparent synthetic resins, and a flat (unbent) flat base material is particularly preferably used.

The thickness of the base material can be appropriately selected according to its use. For example, when the base material is used for a window material or the like,
The thickness of the sheet is preferably from 1 to 100 mm.

[0173]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples. Synthesis Examples (Examples 1 and 2), Examples (Examples 3 to 16),
The present invention will be described based on comparative examples (Examples 17 to 20), but the present invention is not limited thereto. For Examples 3 to 20, a transparent aromatic polycarbonate resin plate (150 mm × 300 mm) having a thickness of 3 mm was used as a base material, and various physical properties were measured and evaluated by the methods described below. Indicated.

(Initial haze value, abrasion resistance) JIS-R321
According to the abrasion resistance test method in No. 2, a haze value was measured with a haze meter when 500 g weights were combined with each of the two CS-10F abrasion wheels and rotated 500 times. The haze was measured at four points of the wear cycle orbit, and the average value was calculated. The initial haze indicates the value (%) of the haze before the abrasion test, and the abrasion resistance indicates the value (%) of (haze after the abrasion test)-(haze before the abrasion test).

(Adhesion) The sample was cut with a razor blade into 11 cuts at intervals of 1 mm each in the vertical and horizontal directions to make 100 grids. Then, after closely attaching a commercially available cellophane tape, the number (m) of the grids remaining without peeling the coating when peeled sharply in the forward direction by 90 degrees is m / 100.
Expressed by

(Abrasion resistance after moisture resistance test)
C. and a relative humidity of 95% for 2 weeks, and then, according to the abrasion resistance test method in JIS-R3212 described above,
The haze was measured in the same manner.

(Weather Resistance) The appearance was evaluated after exposure for 3000 hours using a sunshine weather meter at a black panel temperature of 63 ° C. with a cycle of rainfall of 12 minutes and drying of 48 minutes.

(Bending) The sample was held in a hot air circulating oven at 170 ° C. for 5 minutes, and immediately after being taken out, the sample was pressed into a mold having a curvature of 180 mmR so that the coated surface of the transparent cured material layer was convex, and bent. Processed.

Example 1 Ethyl cellosolve-dispersed colloidal silica (silica content: 30% by weight, average particle size: 11 nm)
5 parts by weight of mercaptopropyltrimethoxysilane and 0.1 part by weight of mercaptopropyltrimethoxysilane.
After adding 3.0 parts by weight of 1N hydrochloric acid, the mixture was heated and stirred at 100 ° C. for 6 hours, and then aged at room temperature for 12 hours to obtain a mercaptosilane-modified colloidal silica dispersion.

Example 2 To 100 parts by weight of colloidal silica dispersed with ethyl cellosolve (silica content: 30% by weight, average particle size: 11 nm), 3-
5 parts by weight of acryloyloxypropyltrimethoxysilane and 3.0 parts by weight of 0.1 N hydrochloric acid were added,
After heating and stirring for an hour, the mixture was aged at room temperature for 12 hours to obtain an acrylsilane-modified colloidal silica dispersion.

Example 3 In a 100 ml four-necked flask equipped with a stirrer and a condenser, 15 g of isopropanol, 15 g of butyl acetate, 7.5 g of ethyl cellosolve, 150 mg of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 150 mg of 2-
(3,5-di-t-pentyl-2-hydroxyphenyl) benzotriazole 1000 mg, 3-acryloyloxypropyltrimethoxysilane 300 mg, and N-methyl-4-methacryloyloxy-2,2,6,6
-200 mg of tetramethylpiperidine was added and dissolved,
Then dipentaerythritol hexaacrylate 1
0.0 g was added and the mixture was stirred at room temperature for 1 hour to obtain a coating composition (hereinafter, referred to as coating liquid 1).

Using a bar coater as a base material, this coating liquid 1
Was applied (wet thickness: 30 μm) and kept in a hot air circulating oven at 80 ° C. for 5 minutes. In an air atmosphere,
2000 mJ / cm ² (wavelength 300) using a high pressure mercury lamp
Ultraviolet light having an integrated energy amount of ultraviolet light in the region of 〜390 nm (the same applies hereinafter) was applied to form a cured product of a transparent coating layer having a thickness of 7 μm.

Next, a xylene solution of perhydropolysilazane (20% by weight, trade name “L110” manufactured by Tonen Co., Ltd.) (hereinafter referred to as Coating Liquid 2)
) Again using a bar coater (wet thickness: 3 μm), and dried in a hot air circulating oven at 80 ° C.
After holding the solvent for 1 minute to remove the solvent, the sample was again irradiated with ultraviolet rays of 2000 mJ / cm ² using a high-pressure mercury lamp in an air atmosphere. Subsequently, the outermost layer was sufficiently hardened by holding in a hot air circulating oven at 100 ° C. for 120 minutes.

[0184] By IR analysis, it was confirmed that the outermost layer was almost completely a silica coating. Thus, a transparent cured product layer having a total film thickness of 7.6 μm was formed on the aromatic polycarbonate resin plate. The above measurement was performed using this sample.

On the other hand, with respect to another sample of the aromatic polycarbonate resin plate having the transparent cured material layer sufficiently cured by using the above coating liquid 1, the abrasion resistance of the surface of the transparent cured material layer was evaluated. . The wear resistance after 100 rotations is 2.7
%Met.

Example 4 The procedure of Example 3 was repeated, except that the sample preparation method was changed as follows. The coating solution 1 was applied and kept in a hot air circulating oven at 80 ° C. for 5 minutes. In an air atmosphere,
Ultraviolet rays of 150 mJ / cm ² were irradiated using a high-pressure mercury lamp to form a cured product of a 7 μm-thick transparent coating layer. The above measurement was performed using this sample.

Example 5 The procedure of Example 4 was repeated, except that the sample preparation method was changed as follows. Finally, instead of holding in a hot air circulating oven at 100 ° C. for 120 minutes, a temperature of 23 ° C. and a relative humidity of 55 were used.
% For one day. The above measurement was performed using this sample.

Example 6 The procedure of Example 3 was repeated, except that the sample preparation method was changed as follows. The coating liquid 2 was changed to a catalyst-free xylene solution of perhydropolysilazane (solids 20% by weight, trade name “V110” manufactured by Tonen Corporation) (hereinafter referred to as coating liquid 3). The above measurement was performed using this sample.

Example 7 The procedure of Example 6 was repeated, except that the sample preparation method was changed as follows. The coating solution 1 was applied and kept in a hot air circulating oven at 80 ° C. for 5 minutes. In an air atmosphere,
Ultraviolet rays of 150 mJ / cm ² were irradiated using a high-pressure mercury lamp to form a cured product of a 7 μm-thick transparent coating layer. The above measurement was performed using this sample.

Example 8 The procedure of Example 7 was repeated, except that the sample preparation method was changed as follows. Finally, instead of holding in a hot air circulating oven at 100 ° C. for 120 minutes, a temperature of 23 ° C. and a relative humidity of 55 were used.
% For one day. The above measurement was performed using this sample.

Example 9 The procedure of Example 8 was repeated, except that the sample preparation method was changed as follows. Finally, instead of curing under an environment of 23 ° C. and a relative humidity of 55% for one day, it was cured by keeping it on a bath of a 3% aqueous solution of triethylamine kept at 25 ° C. for 3 minutes. The above measurement was performed using this sample.

Example 10 In a 100 ml four-necked flask equipped with a stirrer and a condenser, 15 g of isopropanol, 15 g of butyl acetate, 7.5 g of ethyl cellosolve, 150 mg of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 150 mg of 2-
(3,5-di-t-pentyl 2-hydroxyphenyl)
Benzotriazole 1000 mg, hexamethyldisilazane 300 mg, and N-methyl-4-methacryloyloxy-2,2,6,6-tetramethylpiperidine 20
0 mg was added and dissolved, then 10.0 g of dipentaerythritol hexaacrylate was added, and the mixture was stirred at room temperature for 1 hour to obtain a coating composition (hereinafter, referred to as coating liquid 4).

A sample was prepared in the same manner as in Example 3, except that the coating liquid 4 was used instead of the coating liquid 1. The above measurement was performed using this sample.

On the other hand, with respect to another sample of the aromatic polycarbonate resin plate having a transparent cured material layer sufficiently cured by using the above-mentioned coating liquid 4, the abrasion resistance of the surface of the transparent cured material layer was evaluated. 3.1% wear resistance after 100 revolutions
Met.

Example 11 The procedure of Example 10 was repeated, except that the sample preparation method was changed as follows. The coating liquid 4 was applied and kept in a hot air circulating oven at 80 ° C. for 5 minutes. This was irradiated with 150 mJ / cm ² ultraviolet rays using a high-pressure mercury lamp in an air atmosphere to form a cured product of a 7 μm-thick transparent coating layer.
The above measurement was performed using this sample.

Example 12 The procedure of Example 11 was repeated, except that the sample preparation method was changed as follows. Finally, instead of holding in a hot air circulating oven at 100 ° C. for 120 minutes, 23 ° C. and a relative humidity of 5
Cured for one day under 5% environment. The above measurement was performed using this sample.

Example 13 In a 100 ml four-necked flask equipped with a stirrer and a condenser, 15 g of isopropanol, 15 g of butyl acetate, 7.5 g of ethyl cellosolve, 150 mg of 2,4,6-trimethylbenzoyldiphenylphosphine oxide,
(3,5-di-t-pentyl 2-hydroxyphenyl)
Benzotriazole 1000 mg, 3-acryloyloxypropyltrimethoxysilane 300 mg, and N
-Methyl-4-methacryloyloxy-2,2,6,6-
10. Add 200 mg of tetramethylpiperidine to dissolve, and then dipentaerythritol hexaacrylate.
0 g was added and the mixture was stirred at room temperature for 1 hour to obtain a coating composition.
Subsequently, 30.3 g of the mercaptosilane-modified colloidal silica dispersion synthesized in Example 1 was added, and the mixture was further stirred at room temperature for 15 minutes to obtain a coating composition (hereinafter, referred to as coating liquid 5).

Example 5 Using Coating Liquid 5 Instead of Coating Liquid 1
A sample was prepared in the same manner as described above. The above measurement was performed using this sample.

On the other hand, another sample of the aromatic polycarbonate resin plate on which the transparent cured material layer sufficiently cured by using the coating liquid 5 was formed was evaluated for the abrasion resistance of the surface of the transparent cured material layer. Abrasion resistance after 100 rotations is 1.1%
Met.

Example 14 In a 100 ml four-necked flask equipped with a stirrer and a condenser, 15 g of isopropanol, 15 g of butyl acetate, 7.5 g of ethyl cellosolve, 150 mg of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 150 mg of 2-
(3,5-di-t-pentyl 2-hydroxyphenyl)
Benzotriazole 1000 mg, 3-acryloyloxypropyltrimethoxysilane 300 mg, and N
-Methyl-4-methacryloyloxy-2,2,6,6-
10. Add 200 mg of tetramethylpiperidine to dissolve, and then dipentaerythritol hexaacrylate.
0 g was added and the mixture was stirred at room temperature for 1 hour to obtain a coating composition.
Subsequently, 30.3 g of the acrylsilane-modified colloidal silica dispersion synthesized in Example 2 was added, and the mixture was further stirred at room temperature for 15 minutes to obtain a coating composition (hereinafter, referred to as coating liquid 6).

Example 5 using coating liquid 6 instead of coating liquid 1
A sample was prepared in the same manner as described above. The above measurement was performed using this sample.

On the other hand, with respect to another sample of the aromatic polycarbonate resin plate on which the transparent cured material layer was sufficiently cured by using the above coating liquid 6, the abrasion resistance of the surface of the transparent cured material layer was evaluated. . The wear resistance after 100 rotations is 1.2
%Met.

Example 15 The sample adjustment method in Example 4 was changed as follows. The coating liquid 2 is a polysilazane xylene solution in which part of hydrogen on silicon atoms is substituted with a methyl group (solids 20% by weight, trade name “NL710” manufactured by Tonen Corporation) (hereinafter, referred to as “NL710”).
Coating liquid 7). The above measurement was performed using this sample.

Example 16 The sample adjustment method in Example 5 was changed as follows. The coating liquid 1 was applied (wet thickness: 30 μm) using a bar coater and kept in a hot air circulating oven at 80 ° C. for 5 minutes. This is placed in an air atmosphere using a high-pressure mercury lamp.
Irradiation with ultraviolet rays of 50 mJ / cm ² was performed to form a partially cured layer having a thickness of 7 μm. Then, the coating liquid 2 was again coated thereon (wet thickness: 6 μm) using a bar coater, and kept in a hot air circulating oven at 80 ° C. for 5 minutes to remove the solvent. Irradiate ultraviolet rays of 2000 mJ / cm ² using a mercury lamp,
Hold in a hot air circulating oven at 70 ° C. for 5 minutes, and immediately after taking out, 64 m so that the coated surface of the transparent cured product layer is convex.
The sheet was pressed against a mold having a curvature of mR and subjected to bending. Then, as a result of observing the appearance of the product cured at room temperature for one day,
It had a good cured product layer without cracks and wrinkles.

On the other hand, the sample finally obtained in Example 5 and having two fully cured layers was held in a hot air circulating oven at 170 ° C. for 5 minutes, and immediately after being taken out, the coated surface of the transparent cured layer was coated. It was pressed against a mold having a curvature of 64 mmR so as to be on the convex side, and was subjected to bending. As a result of observing the appearance of the obtained sample, cracks and wrinkles were found in the cured product layer.

Example 17 In a 100 ml four-necked flask equipped with a stirrer and a condenser tube, 15 g of isopropanol, 15 g of butyl acetate, 7.5 g of ethyl cellosolve, 150 mg of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 150 mg of 2-
(3,5-di-t-pentyl 2-hydroxyphenyl)
Benzotriazole 1000 mg and N-methyl-4
-200 mg of methacryloyloxy-2,2,6,6-tetramethylpiperidine was added and dissolved, 10.0 g of dipentaerythritol hexaacrylate was added, and the mixture was stirred at room temperature for 1 hour to form a coating composition (hereinafter referred to as coating). Liquid 8) was obtained.

A sample was prepared in the same manner as in Example 3, except that the coating liquid 8 was used instead of the coating liquid 1. The above measurement was performed using this sample.

On the other hand, with respect to another sample of the aromatic polycarbonate resin plate on which the transparent cured material layer sufficiently cured by using the above-mentioned coating liquid 4, the abrasion resistance of the surface of the transparent cured material layer was evaluated. . The wear resistance after 100 rotations is 2.6
%Met.

Example 18 Coating liquid 1 was applied using a bar coater (wet thickness 2
0 μm) and kept in a hot air circulating oven at 80 ° C. for 5 minutes. This is placed in an air atmosphere using a high pressure mercury lamp for 20 minutes.
The transparent cured product layer having a film thickness of 5 μm was cured by irradiating with an ultraviolet ray of 00 mJ / cm ² . The above measurement was performed using this sample.

Example 19 Coating liquid 4 was applied using a bar coater (wet thickness 2
0 μm) and kept in a hot air circulating oven at 80 ° C. for 5 minutes. This is placed in an air atmosphere using a high pressure mercury lamp for 20 minutes.
The transparent cured product layer having a film thickness of 5 μm was cured by irradiating with an ultraviolet ray of 00 mJ / cm ² . The above measurement was performed using this sample.

Example 20 A low-temperature curable solution of perhydropolysilazane in dibutyl ether (solids 20% by weight, trade name “L” manufactured by Tonen Corporation)
120 ”) was applied (wet thickness 3 μm) using a bar coater, kept in a hot air circulating oven at 80 ° C. for 10 minutes to remove the solvent, and then again in an air atmosphere using a high-pressure mercury lamp at 2000 mJ / cm. Irradiation of ultraviolet light of ² .
Subsequently, the outermost layer was sufficiently hardened by holding in a hot air circulating oven at 100 ° C. for 120 minutes. The above measurement was performed using this sample.

[0212]

[Table 1]

From Table 1, it can be seen that each of the samples having a transparent cured material layer according to the present invention of Examples 3 to 15 is different from the sample containing no hydrolyzable silyl group-containing compound (b) (Example 17).
The abrasion resistance after the moisture resistance test, the abrasion resistance after the moisture resistance test and the polysilazane were lower than those of the samples having the coating layer of only the polyfunctional compound (a) (Examples 18 and 19). Abrasion resistance, abrasion resistance after a moisture resistance test, as compared with a sample having a coating layer of only composition (C) containing (c),
It turned out that it is excellent in adhesiveness and weather resistance.
The result of Example 17 is that the coating composition (B) did not contain the hydrolyzable silyl group-containing compound (b), so that the adhesion between the outermost layer and the inner layer was reduced in the moisture resistance test. It seems to be due.

[0214]

As described above, according to the present invention,
The transparent cured material layer (A) has at least two of the outermost layer and the inner layer.
The outermost layer of silica coating is not directly laminated on the relatively soft transparent synthetic resin base material, but is laminated on the hard transparent hard cured inner layer with high abrasion resistance. Therefore, the displacement of the outermost layer due to external force applied to scratch the transparent coated molded product is reduced,
It is possible to obtain surface characteristics that are higher than the surface characteristics provided by ordinary inorganic coatings. The hydrolyzable silyl group-containing compound (b), which has a high affinity for the outermost silica layer, is incorporated into the inner layer network to improve the adhesion between the inner layer and the silica layer. Surface properties such as abrasion and scratch resistance are improved.

According to the present invention having the above-described structure, it is possible to obtain a transparent coated molded article having a surface having high abrasion resistance almost equivalent to that of inorganic glass and having excellent surface properties.

Continued on the front page (72) Inventor Satoshi Kondo 1150 Hazawa-machi, Kanagawa-ku, Yokohama-shi, Kanagawa F-term (reference) in Asahi Glass Co., Ltd. JK09 JK12 JN01 JN01A JN01B JN01C JN30B YY00B 4J038 DL031 DL032 DL081 FA111 FA112 FA131 FA132 FA151 FA152 FA161 FA162 FA171 FA172 FA251 FA252 FA281 FA282 HA446 JC30 JC35 KA03 KA06 KA14 NA01 NA03 PC08 P08

Claims (4)

[Claims] 1. A transparent coated molded article comprising a transparent synthetic resin substrate and a transparent cured product layer (A) provided on at least a part of the surface of the transparent synthetic resin substrate and comprising at least an outermost layer and an inner layer. Of the transparent cured material layer (A),
An active energy ray-curable coating composition in which an inner layer in contact with the outermost layer contains a polyfunctional compound (a) having two or more active energy ray-curable polymerizable functional groups and a hydrolyzable silyl group-containing compound (b). A transparent coated molded article, which is a layer of a cured product of the product (B), wherein the outermost layer is a silica layer which is a cured product of the coating composition (C) containing the polysilazane (c). 2. The coating composition (B) having an average particle size of 20
The transparent coated molded article according to claim 1, which contains colloidal silica having a diameter of 0 nm or less. 3. The cured product of the coating composition (B) is a JI
Number of tests 1 by abrasion resistance test in S-R3212
The transparent coated molded article according to claim 1 or 2, which is a cured product having an abrasion resistance having a haze value of 10% or less after 00 times. 4. A coating composition (C) wherein said polysilazane (c) is at least partially composed of perhydropolysilazane.
The transparent coated molded article according to claim 1, wherein